Composition of matter



Patented Sept. 7, 1943 UNITED STATES PATENT OFFICE I lnin onmthenanawuusmnmmnm- I ester,N.Y.,assignorstoEaetmanKodakOompally, Rochester,

N. Y., a corporation of New Jersey No Drawing. Application January 24, 1940,

7 Serial No. 315,400 g 4 Claims. (CL 260-3) containing two or more synthetic resins. Said composition of matter, according to the invention, may be dissolved in'solvents to form an allpurpose protective coating or may be used as a plastic for the production of molded articles.

Synthetic resins have been used individually as protective coatings and plastics, but when so used have been lacking in heat resistance, have had low chemical and atmospheric corrosion re-- parent to those skilled in the art from the fol-' lowing disclosure.

Our improved composition of matter comprises a mixture or combination of two or more 0! the following resins: a reaction product of a polybasic or alpha-beta-dicarboxylic acid anhydride and terpinene; a hydrocarbon or cycle-olefin resin; a halogenated rubber; and/or a styrol resin.

The reaction product of a polybasic or of an alpha-beta-dicarboxylic acid anhydrlde and terpinene to be employed in the composition according to the invention may be prepared as follows:

Alpha-terpinene may be obtained by the fractionation of pine oil using the fraction boiling within about the range of 178-182 C., and about 480 grams of such alpha-terpinene m y be heated with about 294 gramsof maleic anhydride.

or alternatively with an equivalent quantity" of maleic acid, at a temperature to. cause gentle boiling, say about 150-200 C. for a period of about nve hours. If necessary or desirable, said reaction product may be further pin-model relined by distillation under a diminished pressure by which procedure terplnene and impurities will be rendered volatile and'so removed iron the final reaction product in the still. The preferred reaction product is technically known as hydro phthalic anhydride. Alternatively other alpha-beta-dicarboxylic acid anhydrides may be used for the foregoing synthesis, such as succinic acid anhydride. w

In order further to enhance particular qualities, such as the gloss, flexibility or adhesion, of

' the final composition of matter, said reaction product of a polybasic acid anhydride and terpinene may, if desired, be modified in anyone of several known ways. For instance, said reaction. product may be modified by blending with a dry ing oil, with another synthetic resin, or witha natural resin such as rosin. Such methods of modification may or may not involve the use of heat, or may include the use of a common solvent and the modifying agent may be introduced before or after the reaction is completed, or may constitute the solvent in which the reaction occurs. Preferably and especially for compounding an all-purpose protective coating, said reaction product of a polybasic acid anhydride and terpinene is modified by heating said reaction product together with natural rosin. The hydrocarbon or cyclo-olefln resins to be used are preferably of the coumarone-indene type and may be obtained by thecatalytic polymerization of resin-forming bodies contained in crude solvent naphtha, and other hydrocarbon liquids, containing bodies polymerizable to form resins of the coumarone-indene type.

Specifically, two commercial forms of hydrocarbon resins have been used satisfactorily in the composition of the invention. One a'synthetic hydrocarbon resin" includingdicyclopentadlene and a few per cent of coumarone-indene and known commercially as "G Basin." The other a synthetic hydrocarbon resin including cou-' marone-indene with other polymerizable hydro-- carbons and known commercially as "mum The halogenated rubber to be employed lithe production of the composition in accordance with this invention may be made from raw or yuloenized rubber by any of the methods known for its manufacture. and may be utilised in ,the

chlorinated or brominated state. a chlorinated rubber having a clues-ins context of about 87% will be employed, but'it wilrbe under stood that rubber containing any substantial percentage of chlorine, say as low as 59%. will The viscosity characteristic 0! the chlorinated rubber to be used will depend upon the type oi composition desired. For-locating composition the chlorinated rubber-will preierj ably have a viscosity of from about 5 to, about I-lsopropyl-B- methyl-3,6-indoethylene-M-tetre- 1 10,000 centlpoises in 20% solution in xyloi at 25 C. Where the chlorinated rubber is to he used in the formation of plastics or molded obiects, a much higher viscosity may be used.

The styrol resin may be made by polymerization of styrene to polystyrene and which polymerization may be accomplished lay any of the well known methods or by simply heating the liquid styrene to a temperature apprommately between 200 and 300 C. and holding the material at that temperature until complete polymerization takes place.

When the aforesaid synthetic resins are mixed in the combinations and proportions disclosed herein, compositions of matter having remarkable characteristics are obtained. A composition of matter comprising a physical mixture of 35-65 parts of a reaction product of a polybaslc acid anhydride and terpinene and 65-35 parts of a hydrocarbon resin has good hardness, flexibility and chemical corrosionresistance. A composition of matter of similar properties but of even greater chemical corrosion resistance comprises a physical mixture of 10-30 parts of a reaction product of a polybasic acid anhydride and terpinene, 30-50 parts of a hydrocarbon resin, and 60-40 parts oi halogenated rubber. However, a composition of matter having good flexibility and excellent gloss is obtained by eliminating said hydrocarbon resin from the aforementioned three component mixture and by physically com bining together 10-40 parts of the reaction product of a polybasic acid anhydrlde and terpinene and 50-10 parts of halogenated rubber. also a composition having outstanding chemical resistonce is obtained by omitting the reaction product from said three component mixture one. by physically mixing 10-40 parts of hydrocarbon resin and 50-10 parts of halogenated rubber.

A. composition of matter exceptional hardness, good flexibility, and chemical and weather corrosion resistance comprises physical mixture of iii-30 parts of the reactlonprcduct of a polybasic acid anhydride and terpinene, 20-40 parts of a hydrocarbon resin, and iii-59 parts of a polystyrol resin, By eliminating; the hydrocarbon resin and compounding EG-tll parts of a reaction product of a polyoasic anhyrlride and terpinene with 80-20 parts of polystyrene, a composition of matter is obtained which has good hardness and adhesion and which lies particularly good weather resistance. Uri the other hand, the reaction product may be omitted from said three component mixture, such composition of matter will then comprise a physical mixture of 20-80 partsof a hydrocarbon resin and coco parts of polystyrene, has improved hardness and chemical resistance and protective coating: solutions made therefrom may be more easily applied.

Example 1 Al. ccmr sition of matter compzisins a reaction product of alpnc heta dicarooxylic ascascc dride and terpinene and a l'iydrocaroen resin is preferably prepared by physically mixing equal parts of the reaction product of roaleic acid anhydride with alpha-terpinene and either of said cycle-olefin resins. To form a lacquer, the mixture may be dissolved in a suitable quantity of a solvent; such as a solvent comprising 50% toluene, 25% xylene, 12%% aznyl acetate, and 12%% coal tar solvent naphtha. The resulting solution is a clear lacquer which is stable for storage. The film formed from this lacouer possesses excellent gloss, and is durable for interior use.

Example 2 The composition of matter comprising a reaction product of elpha-betacliearboxylic acid anhydride and alpha=terpinene, a hydrocarbon resin, and halogenated rubber is preferably prepared by physically mixing to parts oi chlorinated rubber, 40 parts of the cycle-olefin resin and as parts of the reaction product of models acid anhydride and alpha-terpinene. For use as a coating, the foregoing mixture is dissolved in a suitable quantity of the solvent mixture mentioned in; Example 1 to form a clear lacquer which give a film of outstanding corrosion resistance. However, such corrosion resistance is considerably enhanced by the addition of Ellparts oi a suitable inert pigment, such as graphite or titanium dioxide, and grindin for as to es hours in a. standard ball mill.

if aprotective coating or plmtic of greater hardness and/or adhesion to metal is desired, the cycle-olefin resin may he eliminated from this Example 2 to give a composition of matter comprising a physical mixture equal parts of a reaction product of maleio acid anhydricle and elplia terpinene and of chlorinated rubber, either in a suitable solvent minute or in a properly elasticized solid state,

0n the other hand, if a protective coating or plastic possessing extreme resistance to prolonged immersion in aqueous solutions oi various reagents is reeuireci, the reaction product of maleic acid anhydrlde and alpha terpinene may be omitted from this Example 2 to give a com position of matter comprising a homogeneous physical mixture of corral parts of chlorinated rubber and cycle-olefin. resin which may be dissolved or plasticizeel to provide a soft and pliable protective coating or plastic.

Example 3 The composition of matter according to the in vention and comp-rising a reaction product of alnl1a=l1eta-dicarboxylic acid anhydricle and alpha-terpinene, a hydrocarbon resin, and a styrol resin. is preferably prepared by physically,

mixing as parts of the reaction product of maleic acid anhyolride and alpha-teroinene, as parts of cycle-olefin resin and 6% parts of polystyrene. For use as a lacquer, said mixture may be dissolve-g; in an adequate quantity of the solvent combination of llbzample l. or an equivalent solvent. Films formed of such lacquer are exceptionally hard, and have great resistance to corrosion. However, such corrosion resistance is markedly increased when the cycle-olefin resin i in the form. of dicyclepentediene. Films formed iroin this modified mixture have been to resist the action of strong oxidizing reagent, notably silver nitrate solution.

ll. a protective coating or plastic of equivalent weather resistance and good heat resistance is the hydrocarbon en may be omitted asaaoee and a composition 01 matter is prepared prefera'bly by mixing equal parts oi. the reaction product of a polybasic acid anhydride and a terpinene and of polystyrene. n the other hand. a composition or good chemical corrosion resistance and readily applied as a lacquer is composed of a homogeneous physical mixture preferably of equal parts of polystyrene and the dicyclopentadiene type of hydrocarbon resin.

Although the solvent mixture herein disclosed has been very successfully employed, it is to be understood that the ingredients and proportions of the mixtures may be varied considerably within the ranges given, and for instance it slow drying films or slow drying adhesives are required the solvent mixture may be modified by the addition or substitution oi comparatively high boiling solvents which are compatible with the other ingredients used. On the other hand, as is known, quick drying films or adhesives are obtained by the addition or substitution of comparatively low boiling solvents to the solvent mixture.

Having now particularl described our invention, what we desire to secure by Letters Patent of the United States and we claim is:

1. As a composition or matter, a physical mixture comprising 10-30 parts of reaction product of an alpha-beta-dicarboxylic acid anhydride and terpinene, -50 parts of a coumarone-indene cyclo-oleilne resin, and 60-40 parts of a haloaenated rubber.

2. As a commition of matten'a physical mixture comprising 10-30 parts or a reaction product base for a protective coating, a physical mixture comprising 10-30 parts of a reaction product of maleic anhydride and alpha-terpinene, 30-50 parts of dicyclopentadiene resin, 60-40 parts of a chlorinated rubber, and an organic solvent for said ingredients. I

4. A a composition of matter according to' claim 1, ahomogeneous mas comprising a Physical mixture substantially of 20 parts of a modified reaction product of an aJpha-beta-dicarboxylic acid anhydride and terpinene, 40 parts ,0! a

coumarone-indene cyclo-olenne resin and parts 01 a chlorinated rubber.

ravnla c. ua'rnmws. WILLIAM F. mmcn. 

